JPH0577363A - Glass run channel - Google Patents

Abstract

PURPOSE:To simplify a manufacturing process and to enhance durability and airtightness by using a laminate wherein a layer consisting of an ultrahigh mol.wt. polyolefin composition and a lubricating resin is laminated to a plyolefinic thermoplastic elastomer layer in the window glass sliding part on the surface of a drain part. CONSTITUTION:The contact part 4 of the surface of the drain part 3 of a glass run channel 1 made of a polyolefinic thermoplastic elastomer with window glass is formed by laminating a layer consisting of an ultrahigh mol.wt. polyolefin composition and a lubricating resin to an elastomer layer The ultrahigh mol.wt. polyolefin composition contains 90-10 pts.wt. of ultrahigh mol.wt. polyolefin with intrinsic viscosity (n) of 6dl/g or more and 10-90 pts.wt. of polyolefin with intrinsic viscosity (n) of 0.1-5dl/g and at least one of both polyolefins is modified with a modifying monomer being unsaturated carboxylic acid or a derivative thereof. The lubricating resin is selected from either one of a polyamide resin, a thermoplastic polyurethane resin and a thermoplastic polyester resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass run channel, and more particularly to a glass run channel provided with a window glass sliding portion formed of a laminate composed of a thermoplastic elastomer substrate layer and a slip resin surface layer. Regarding the channel.

[0002]

BACKGROUND OF THE INVENTION Generally, a window glass in a vehicle of an automobile needs to be opened and closed by raising and lowering for ventilation ventilation or for communication with the outside of the vehicle. It is called a glass run channel between the window glass and the window frame in order to facilitate the up-down opening / closing operation of the window glass and also to enable the tight (liquid-tight) sealing operation between the window glass and the window frame. A guide member is provided.

A conventional glass run channel is a groove-shaped main body formed by a soft synthetic resin such as a soft vinyl chloride resin or a vulcanized rubber such as an ethylene-propylene-diene copolymer rubber, and a groove-shaped main body thereof. It consists of a tongue-shaped drainer that extends from the top of the side wall toward the center.

In the conventional glass run channel, a nylon film or the like is formed on the surface of the window glass sliding portion in order to make the drainer part away from the sliding part with the window glass good and to prevent the window glass from being soiled. Glued together,
Further, in order to reduce the contact area with the window glass, embossing is performed before or after laminating the nylon film or the like.

In the conventional glass run channel, since there is no adhesiveness between the soft synthetic resin or vulcanized rubber described above and the surface material such as nylon, the body of the glass run channel is molded with the soft synthetic resin or vulcanized rubber. Then, a step of applying an adhesive to the obtained molded product and laminating a film such as nylon is necessary, and further, embossing must be performed before or after this adhesion,
There is an inconvenience that the number of steps is large and labor is required.

Further, in the conventional glass run channel,
Since there is a step of laminating with an adhesive, there is also a problem in durability, and there is also the drawback that peeling easily occurs between the surface film layer and the substrate due to aging and outdoor exposure. Furthermore, the concavo-convex pattern that can be formed by embossing is still not sufficiently satisfactory in the combination of fineness and uniformity, and the close contact property between the sliding portion of the window glass and the window glass at the time of closing and the opening at the time of opening There is still room for improvement in the light sliding property between the window glass sliding portion and the window glass.

[0007] Therefore, the inventors of the present invention conducted extensive studies to solve the above problems of the glass run channel, and selected a polyolefin-based thermoplastic elastomer as the elastomer constituting at least the window glass sliding portion of the glass run channel. Then, if the ultrahigh molecular weight polyolefin composition and the slip resin are laminated by heat fusion on the polyolefin-based thermoplastic elastomer layer, the manufacturing work is easy, and the durability and the window glass when closed are The inventors have found that it is possible to obtain a glass run channel having excellent close contact properties and light sliding properties with respect to a window glass when opened, and have completed the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, can be manufactured by simplifying the manufacturing process, and has durability and window glass when closed. It is an object of the present invention to provide a glass run channel which is excellent in close contact property with the above and in light sliding property with respect to the window glass when opened.

[0009]

SUMMARY OF THE INVENTION A glass run channel according to the present invention comprises:
A glass run channel made of a polyolefin-based thermoplastic elastomer, which is composed of a groove-shaped main body in a cross section and a tongue-shaped drainer extending from the vicinity of the top of the side wall toward the center side. At least a portion of the surface that can come into contact with the window glass is composed of a layer composed of an ultra-high molecular weight polyolefin composition and a slip resin, which is laminated on a polyolefin-based thermoplastic elastomer layer, and the ultra-high molecular weight polyolefin composition has (A ) Ultra-high molecular weight polyolefin 9 having an intrinsic viscosity [η] of 6 dl / g or more
0 to 10 parts by weight and (B) the intrinsic viscosity [η] is 0.1 to 5
10 to 90 parts by weight of dl / g polyolefin, and the ultrahigh molecular weight polyolefin (A) and / or polyolefin (B) is at least one selected from unsaturated carboxylic acids and their derivatives. An ultrahigh molecular weight polyolefin composition modified with a modifying monomer (C), wherein the slip resin is a slip resin selected from the group consisting of a polyamide resin, a thermoplastic polyurethane resin, and a thermoplastic polyester resin. It is characterized by being.

In the present specification, the term "polyolefin-based thermoplastic elastomer" may refer not only to a non-graft-modified polyolefin-based thermoplastic elastomer but also to a graft-modified polyolefin-based thermoplastic elastomer. is there.

[0011]

DETAILED DESCRIPTION OF THE INVENTION An example of the glass run channel according to the present invention will be specifically described below with reference to the drawings.

In FIG. 1, which shows a cross-sectional structure of an example of the glass run channel of the present invention, the glass run channel 1 has a groove-shaped (U-shaped) main body 2 in a horizontal cross section, and a center from the vicinity of the top of the side wall portion It is composed of a tongue-shaped water draining portion 3 protruding toward the side. The pair of draining portions 3 and 3 extend inwardly in the groove of the main body 2, and the outer surface side of the pair of draining portions 3 and 3 serves as a window glass contact portion 4. It is in a positional relationship. The main body 2 is provided with a hook 6 for attaching to the window frame on the outer wall thereof.

Although the main body 2 and the draining portion 3 are integrally formed of an elastomer, according to the present invention, at least the window glass contact portion 4 and the base layer made of a thermoplastic polyolefin-based elastomer and the ultrahigh molecular weight polyolefin composition are used. And a slipping resin layer made of a slipping resin. As shown in FIG. 2 in which the window glass contact portion 4 is enlarged, the surface 8 of the base layer 7 made of a thermoplastic polyolefin-based elastomer is preferably provided with a repeating pattern of fine irregularities. On the surface 8 having such a sharkskin-like fine concavo-convex pattern, a slipping resin layer 9 made of an ultrahigh molecular weight polyolefin composition and a slipping resin is laminated by heat fusion, and the outer surface 10 has the same shape. It is preferable that the repetitive pattern of fine irregularities of is applied.

In FIGS. 3, 4 and 5 for explaining the mounting of the glass run channel to an automobile,
A window glass 12 is provided on a door 11 of an automobile so that it can be opened and closed by raising and lowering, while a glass run channel 1 is fixed to a window frame 13. That is, in FIG. 4 and FIG. 5, the window frame 13 has a U-shaped cross section as a whole, and an inwardly projecting portion 15 is formed at the entrance of the recess 14. The glass run channel 1 is fixed to the window frame 13 by inserting the glass run channel 1 into the recess 14 and engaging the engaging hook 6 with the projection 15. As shown in FIG. 4, when the window glass 12 is lowered, the tips 5 and 5 of the glass sliding portions are closed to face each other, and as shown in FIG. 5, the window glass 12 is in the raised state. Then, the tips 5 and 5 of the window glass sliding portion are separated by the window glass 12 fitted between them, but are in contact with the window glass surface.

According to the invention, the glass run channel 1
Among these, a base layer 7 made of a thermoplastic polyolefin-based elastomer at least in a portion that comes into contact with a window glass, and a slippery resin layer made of an ultrahigh molecular weight polyolefin composition heat-sealed to the surface of the base layer 7 and a slipping resin. And 9 are provided.

That is, the polyolefin-based thermoplastic elastomer used in the present invention can be thermoformed into any shape and size, and the elasticity and flexibility required for the window glass sliding portion of the glass run channel. ,
It has excellent properties such as compressibility, and also has excellent properties such as durability, weather resistance, and water resistance. This polyolefin-based thermoplastic elastomer may be modified by graft copolymerization of a polar group-containing monomer such as maleic anhydride. The thermoplastic polyolefin-based elastomer exhibits strong adhesiveness to the slip resin layer 9 made of the ultra-high molecular weight polyolefin composition and the slip resin, which is the surface material layer, and by heat fusion with the slip resin layer 9, It is possible to form a laminated structure having excellent interlaminar adhesive strength immediately after adhering and over time, and further, excellent interlaminar adhesive strength after a weathering test. Moreover, the thermoplastic polyolefin-based elastomer used as the base layer 7 in the present invention can be molded so as to have a sharkskin-like molded appearance.
By combining this molding step and the heat-sealing step of the lubrication resin layer 9 made of the ultrahigh molecular weight polyolefin composition and the lubrication resin as the surface material layer and the base layer 7, the lubrication resin layer 9 It is also possible to faithfully reproduce a sharkskin-like fine uneven pattern on the outer surface. It is extremely difficult to copy such a sharkskin-like surface with fine irregularities by the conventional adhesive coating method, and it has become possible only by combining the above-mentioned molding step and heat fusion step.

According to the present invention, by adopting the above-mentioned configuration, the adhesive applying step, the adhesive curing or baking step, and the embossing step before or after the adhesive step are all omitted, and the number of steps is small and the number is small. The glass run channel can be efficiently manufactured with time and effort. Further, by providing the slipping resin layer 9 composed of the ultra high molecular weight polyolefin composition and the slipping resin as the surface material layer, not only the coefficient of friction with the window glass can be reduced, but also the concavo-convex pattern formed by the conventional embossing process can be achieved. As compared with the pattern, it became possible to form sharkskin-like fine irregularities on the surface with a uniform pitch. Therefore, in the glass run channel according to the present invention, when the window glass is closed, it is possible to make a tight (liquid-tight) contact with the window glass, and when the window glass is opened, the sliding resistance thereof is reduced so that the glass run channel is smooth and light. Opening and closing operations are possible.

Polyolefin Thermoplastic Elastomer The polyolefin thermoplastic elastomer used in the present invention is composed of crystalline polyolefin and rubber.

Examples of the crystalline polyolefin used in the present invention include homopolymers or copolymers of α-olefins having 2 to 20 carbon atoms. Specific examples of the crystalline polyolefin include the following (co) polymers. (1) Ethylene homopolymer (manufacturing method may be either low pressure method or high pressure method) (2) Copolymerization of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate or ethyl acrylate Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10 mol% or less of other α-olefins (5) Block copolymerization of propylene and 30 mol% or less of other α-olefins Combined (6) 1-butene homopolymer (7) Random copolymer of 1-butene and other α-olefin at 10 mol% or less (8) 4-Methyl-1-pentene homopolymer (9) 4 -Methyl-1-pentene and other α up to 20 mol%
-Random copolymer with olefin As the above α-olefin, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Examples include hexene and 1-octene.

The rubber used in the present invention is not particularly limited, but an olefin copolymer rubber is preferable. The above olefin-based copolymer rubber has 2 to 20 carbon atoms.
Amorphous random elastic copolymer containing α-olefin as a main component, which is an amorphous α-olefin copolymer composed of two or more α-olefins, and non-conjugated with two or more α-olefins Examples include α-olefin / non-conjugated diene copolymers composed of diene.

Specific examples of such an olefinic copolymer rubber include the following rubbers. (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10 to 50 /
50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90
/ 10 to 50/50] (3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90/10 to 5
0/50] (4) Butene / α-olefin copolymer rubber [butene /
α-olefin (molar ratio) = about 90/10 to 50/5
0] Specific examples of the α-olefin include the same α-olefins as the specific examples of the α-olefin constituting the crystalline polyolefin component described above.

As the non-conjugated diene, specifically,
Examples thereof include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene.

Mooney viscosity ML of these copolymer rubbers
_{1 + 4} (100 ° C) is 10 to 250, especially 40 to 150
Is preferred. The iodine value when the non-conjugated diene is copolymerized is preferably 25 or less.

The above-mentioned olefinic copolymer rubber can exist in all crosslinked states such as uncrosslinked, partially crosslinked and totally crosslinked in the thermoplastic polyolefin elastomer, but in the present invention, it is partially crosslinked. It is preferably present in a state.

The rubber used in the present invention includes:
In addition to the above olefin copolymer rubber, other rubber,
For example, styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), butyl rubber (I
IR) and other diene rubbers, SEBS, polyisobutylene, and the like.

In the thermoplastic polyolefin-based elastomer used in the present invention, the weight blending ratio of crystalline polyolefin and rubber (crystalline polyolefin / rubber) is
90/10 to 10/90, preferably 70/30 to 2
The range is 0/80.

When a combination of an olefin copolymer rubber and other rubber is used as the rubber, the other rubber is 1 in the total amount of the crystalline polyolefin and the rubber.
40 parts by weight or less, preferably 5 to 100 parts by weight
It is mixed in a ratio of 20 parts by weight.

The thermoplastic polyolefin-based elastomer preferably used in the present invention comprises a crystalline polypropylene and an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber. A thermoplastic elastomer which is present in a partially crosslinked state in an elastomer and has a weight compounding ratio of crystalline polypropylene and rubber (crystalline polypropylene / rubber) within a range of 70/30 to 20/80. is there.

In the thermoplastic polyolefin elastomers mentioned above and below, if necessary, mineral oil softeners, heat stabilizers, antistatic agents, weather stabilizers, antiaging agents, fillers, colorants, lubricants, etc. The additive can be added within a range that does not impair the object of the present invention.

More specific examples of the polyolefin-based thermoplastic elastomer preferably used in the present invention include:
Rubber (b) 40 to 9 comprising 60 to 10 parts by weight of crystalline polypropylene (a) and ethylene / propylene copolymer rubber or ethylene / propylene / diene copolymer rubber
0 parts by weight [the total amount of components (a) and (b) is 100
Parts by weight] and 5 to 100 parts by weight of a rubber (c) other than the rubber (b) and / or a mineral oil-based softening agent (d) are dynamically heat treated in the presence of an organic peroxide. The polyolefin-based thermoplastic elastomer obtained by partially crosslinking the rubber (b) is obtained.

Specific examples of the above organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di- (tert-butylperoxy).
Hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)- 3,3,5-Trimethylcyclohexane, n-butyl
-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, Diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like can be mentioned.

Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-from the viewpoint of odor and scorch stability. (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 1,4-bis (tert-butylperoxy) valerate is preferred, and among them, 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

In the present invention, the organic peroxide is
It is used in a proportion of 0.05 to 3% by weight, preferably 0.1 to 1% by weight, based on 100% by weight of the total amount of the crystalline polyolefin and rubber.

In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime and N-methyl-N are used in the partial crosslinking treatment with the above organic peroxide.
-4- Dinitrosoaniline, nitrosobenzene, diphenylguanidine, peroxy crosslinking aids such as trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, A polyfunctional methacrylate monomer such as diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, or a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate can be added.

By using the above compound,
A uniform and mild crosslinking reaction can be expected. Particularly, divinylbenzene is most preferable in the present invention. Divinylbenzene is a dispersant for organic peroxides, which is easy to handle, has good compatibility with the crystalline polyolefin and the rubber which are the main components of the above-mentioned substance to be crosslinked, and has the action of solubilizing organic peroxides. As a result, a thermoplastic elastomer having a uniform cross-linking effect by heat treatment and a good balance of fluidity and physical properties can be obtained.

In the present invention, the above-mentioned crosslinking aid or polyfunctional vinyl monomer is contained in an amount of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the total amount of the above-mentioned object to be crosslinked. It is preferable to use it in a ratio of. When the blending ratio of the cross-linking aid or the polyfunctional vinyl monomer exceeds 2% by weight, when the blending amount of the organic peroxide is large, the crosslinking reaction proceeds too fast. Inferiority, on the other hand, when the blending amount of the organic peroxide is small, the crosslinking aid and the polyfunctional vinyl monomer remain as an unreacted monomer in the polyolefin-based thermoplastic elastomer, and the polyolefin-based thermoplastic elastomer is Changes in physical properties may occur due to heat history during processing and molding. Therefore,
The cross-linking aid and polyfunctional vinyl monomer should not be blended in excess.

The above-mentioned "dynamically heat treating" means kneading each of the above components in a molten state. As the kneading device, a conventionally known kneading device such as an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader or a continuous mixer can be used. Of these, a non-open type kneading device is preferable, and kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The kneading is preferably carried out at a temperature at which the half-life of the organic peroxide used is less than 1 minute.
The kneading temperature is usually 150 to 280 ° C., preferably 170
To 240 ° C., and the kneading time is 1 to 20 minutes, preferably 3 to 10 minutes. Also, the shearing force applied is
The shearing force is usually 10 to 10 ⁴ sec ^-1 , preferably 10
It is determined within the range of ² to 10 ³ sec ^-1 .

The preferred thermoplastic polyolefin-based elastomer used in the present invention is partially crosslinked, and the term "partially crosslinked" means that the gel content measured by the following method is 20 to 98%. In the present invention, the gel content is preferably within the range of 45 to 98%.

[Measurement Method of Gel Content] As a sample, about 100 m of pellets of polyolefin thermoplastic elastomer are used.
g Weigh precisely and immerse in a closed container in 30 ml of cyclohexane, a sufficient amount for this pellet, at 23 ° C. for 48 hours.

Next, this sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. The gel content is represented by the following formula. Gel content [%] = (dry weight after immersion in cyclohexane)
÷ (Weight before dipping in cyclohexane) × 100 In the present invention, the following modified polyolefin thermoplastic elastomer (MTPE) can be used as a preferable polyolefin thermoplastic elastomer constituting the base layer 7. .. (I) Peroxide cross-linking type olefin copolymer rubber 9
5 to 10 parts by weight, and (ii) olefin-based plastic 5
~ 90 parts by weight [the total amount of components (i) and (ii) is 1
00 parts by weight] and (iii) 0.01 to 10 parts by weight of a polar group-containing monomer such as an α, β-unsaturated carboxylic acid or its derivative, or an unsaturated epoxy monomer. Is a modified polyolefin-based thermoplastic elastomer that has been partially cross-linked by being dynamically heat-treated in the presence of an organic peroxide.

The peroxide-crosslinking olefin copolymer rubber (i) used in the present invention is, for example, ethylene.
Amorphous elastic copolymers containing olefin as the main component, such as propylene / non-conjugated diene copolymer rubber and ethylene / butadiene copolymer rubber, which must be mixed with organic peroxide and kneaded under heating. Means a rubber that is crosslinked to reduce the fluidity or does not flow.

Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene-norbornene and ethylidene-
Examples include norbornene.

In the present invention, among the above-mentioned peroxide-crosslinking type olefin copolymer rubbers, the molar ratio of ethylene component unit to propylene component unit (ethylene component unit / propylene component unit) is 50/50 to 50%. 90/1
Ethylene / propylene copolymer rubbers and ethylene / propylene / non-conjugated diene copolymer rubbers, which are 0, particularly in the range of 55/45 to 85/15, are preferably used. Among them, ethylene / propylene / non-conjugated diene copolymer rubber, particularly ethylene / propylene / ethylidene norbornene copolymer rubber is preferable in that it can provide a thermoplastic elastomer excellent in heat resistance, tensile strength characteristics and impact resilience.

The peroxide crosslinked olefin copolymer rubber has a Mooney viscosity ML _{1 + 4} (100 ° C.) of 1
It is preferably in the range of 0 to 250, particularly 40 to 150. When a peroxide-crosslinking olefin-based copolymer rubber having a Mooney viscosity ML _{1 + 4} (100 ° C.) of less than 10 is used, the thermoplastic elastomer composition obtained tends to have reduced tensile strength properties. On the other hand, Mooney viscosity M
When a peroxide-crosslinking olefin-based copolymer rubber having an L _{1 + 4} (100 ° C.) of more than 250 is used, the thermoplastic elastomer composition obtained tends to have reduced fluidity.

Further, the peroxide-crosslinking olefin copolymer rubber preferably has an iodine value of 25 or less. When the peroxide-crosslinking olefin-based copolymer rubber having an iodine value within the above range is used, a thermoplastic elastomer having a good balance of fluidity and rubber-like properties can be obtained.

In the present invention, the peroxide-crosslinking olefin-based copolymer rubber (i) is added to the peroxide-crosslinking olefin-based copolymer rubber (i) and the olefin-based plastic (ii) in an amount of 100 parts by weight. , 9
It is used in an amount of 5 to 10 parts by weight, preferably 95 to 60 parts by weight.

When the peroxide-crosslinking olefin-based copolymer rubber (i) is used in the above proportion, the resulting graft-modified polyolefin-based elastomer has excellent moldability and rubber properties such as rubber elasticity. ing.

The olefinic plastic (ii) used in the present invention comprises a crystalline, high molecular weight solid product obtained by polymerizing one or more monoolefins by either the high pressure method or the low pressure method. Examples of such resins include isotactic or syndiotactic monoolefin polymer resins. These representative resins are commercially available.

Specific examples of suitable raw material olefins include ethylene, propylene, 1-butene, 1-pentene, 1-
Hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-
Examples include octene, 1-decene and mixed olefins of two or more of these. In the present invention, any polymerization method may be adopted whether it is homopolymerization or copolymerization as long as a resinous material is obtained.

In the present invention, a particularly preferable olefin-based plastic is a peroxide decomposition type olefin-based plastic. In the present invention, the peroxide-decomposable olefin-based plastic refers to an olefin-based plastic in which the fluidity of the resin is increased by reducing the molecular weight by thermally decomposing by mixing with peroxide and kneading with heating. Tactic polypropylene; a copolymer of propylene and a small amount of other α-olefin, such as propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl -1-Pentene copolymer and the like can be mentioned.

The olefinic plastic used in the present invention has a melt index (ASTM-D-1238).
-65T, 230 ° C) is preferably in the range of 0.1 to 50, particularly 5 to 20.

In the present invention, the olefinic plastic contributes to the improvement of the fluidity and heat resistance of the elastomer composition. In the present invention, the olefin plastic (ii) is 5 to 90 parts by weight based on 100 parts by weight of the total amount of the peroxide-crosslinking olefin copolymer rubber (i) and the olefin plastic (ii).
It is used in a proportion of parts by weight, preferably 5 to 40 parts by weight.

When the olefin-based plastic (ii) is used in the above proportion, the resulting graft-modified polyolefin-based elastomer has excellent rubber-like properties such as rubber elasticity and excellent flowability, resulting in molding. It has excellent properties.

In the present invention, examples of the modifying agent (iii) used for graft-modifying the polyolefin thermoplastic elastomer include α, β-unsaturated fatty acids or derivatives thereof, and monomers such as unsaturated epoxy monomers. Be done.

Specific examples of the α, β-unsaturated fatty acid or its derivative include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid; maleic anhydride, itaconic anhydride, Acid anhydrides such as norbornene carboxylic anhydride and tetrahydrophthalic anhydride; hydroxyalkyl esters or hydroxyalkoxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate and hydroxyethoxymethacrylate. .. In the present invention, maleic anhydride and hydroxyethyl acrylate are preferably used.

Specific examples of unsaturated epoxy monomers include glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate and glycidyl crotonate. In the present invention, glycidyl methacrylate is preferably used.

In addition, the above "dynamic heat treatment", kneading apparatus,
The kneading conditions and “partial cross-linking” are the same as in the case of the above-mentioned non-graft-modified polyolefin-based thermoplastic elastomer.

The thermoplastic polyolefin-based elastomer used in the present invention is excellent in fluidity because it comprises crystalline polyolefin and rubber. Further, the body 2 of the glass run channel made of the thermoplastic polyolefin-based elastomer and the base layer 7 of the draining portion 3 are excellent in rubber properties such as heat resistance, tensile properties, flexibility and anti-elasticity. In the present invention, the partially crosslinked non-graft modified polyolefin thermoplastic elastomer and the partially crosslinked graft modified polyolefin thermoplastic elastomer as described above are preferable.

The above-mentioned thermoplastic polyolefin-based elastomer can be molded using a conventionally used molding apparatus such as compression molding, transfer molding, injection molding or the like.

Ultra High Molecular Weight Polyolefin Composition The ultra high molecular weight polyolefin composition used in the present invention contains 90 to 10 parts by weight of an ultra high molecular weight polyolefin (A) having an intrinsic viscosity [η] of 6 dl / g or more and an intrinsic viscosity [[ η]
Of 0.1 to 5 dl / g polyolefin (B) 10 to 9
And at least one modifying monomer (C) selected from unsaturated carboxylic acids and their derivatives as the ultrahigh molecular weight polyolefin (A) and / or polyolefin (B). ) Has been modified.

The above-mentioned ultra high molecular weight polyolefin (A)
Is, for example, ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-
Butene, 1-hexene, 3-methyl-1-pentene, 4-methyl
-1-Pentene, 1-heptene, 1-octene, 1-decene, 1-
It consists of an α-olefin homopolymer or copolymer such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosene. In the present invention, ethylene homopolymers and ethylene-based copolymers composed of ethylene and other α-olefins are preferred.

The intrinsic viscosity [η] of this ultrahigh molecular weight polyolefin (A) measured at 135 ° C. in a decalin solvent was 6
dl / g or more, preferably 6 to 40 dl / g, and more preferably 10 to 30 dl / g. In the present invention, especially the density (D: ASTM D1505) is 0.920 g / c.
m ³ or more, melting point (Tm: ASTM D 3417) is 11
An ultra high molecular weight polyolefin having a temperature of 5 ° C. or higher is preferable.

In the present invention, the ultrahigh molecular weight polyolefin (A) is 90 to 10 parts by weight, preferably 80 to 10 parts by weight based on 100 parts by weight of the total amount of the ultrahigh molecular weight polyolefin (A) and the polyolefin (B). 10 parts by weight,
More preferably, it is used in a proportion of 50 to 10 parts by weight.

The polyolefin (B) which is a constituent of the ultra high molecular weight polyolefin composition is the same as the above ultra high molecular weight polyolefin (A) from the homopolymer or copolymer of the α-olefin as described above. Become. In the present invention, ethylene homopolymers and ethylene-based copolymers composed of ethylene and other α-olefins are preferred.

The intrinsic viscosity [η] of this polyolefin (B) measured at 135 ° C. in a decalin solvent is 0.1 to 5 d.
It is 1 / g, preferably 0.3 to 4 dl / g. In the present invention, a polyolefin having a density of 0.92 to 0.97 g / cm ³ and a melting point of 115 to 145 ° C. is particularly preferable.

In the present invention, 10 parts by weight of the above polyolefin (B) is added to 100 parts by weight of the total amount of the ultrahigh molecular weight polyolefin (A) and the polyolefin (B).
To 90 parts by weight, preferably 20 to 90 parts by weight, more preferably 50 to 90 parts by weight.

In the present invention, the ultrahigh molecular weight polyolefin (A) is used within the above range depending on the molding method.
The content ratio of the polyolefin (B) can be adjusted. For example, when the above ultrahigh molecular weight polyolefin composition is used for injection molding, the total amount of the ultrahigh molecular weight polyolefin (A) and the polyolefin (B) is 10
Ultra high molecular weight polyolefin (A) is 25 to 10 parts by weight, and polyolefin (B) is 75 to 90 parts by weight relative to 0 parts by weight.
It is preferable to use the ultrahigh molecular weight polyolefin composition which is present in a ratio of parts by weight, because moldability and a good appearance can be obtained. When the above ultrahigh molecular weight polyolefin composition is used for extrusion molding, the total amount of the ultrahigh molecular weight polyolefin (A) and the polyolefin (B) is 10
80 to 15 parts by weight of ultra-high molecular weight polyolefin (A) and 20 to 85 parts by weight of polyolefin (B) relative to 0 parts by weight.
It is preferable to use the ultrahigh molecular weight polyolefin composition which is present in a ratio of parts by weight, because moldability and a good appearance can be obtained.

In the ultrahigh molecular weight polyolefin composition used in the present invention, the ultrahigh molecular weight polyolefin (A)
And / or the unsaturated carboxylic acid which is the modifying monomer (C) for modifying the polyolefin (B),
Specifically, acrylic acid, methacrylic acid, maleic acid,
Examples include fumaric acid, itaconic acid, citraconic acid, crotonic acid, endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^TM ).

The derivatives thereof include acid halides,
Esters, amides, imides, anhydrides, and the like, specifically, maleenyl chloride, maleimide, acrylic acid amide, methacrylic acid amide, glycidyl methacrylate,
Examples thereof include maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. These modifying monomers (C) may be used alone or in combination of two or more. Among these, maleic anhydride is preferable because it has high reactivity and a molded product having good strength and appearance can be obtained.

The ultrahigh molecular weight polyolefin composition used in the present invention comprises a composition containing the above ultrahigh molecular weight polyolefin (A) and polyolefin (B). In this composition, the ultrahigh molecular weight polyolefin (A) and And / or the polyolefin (B) is modified with at least one modifying monomer (C) selected from unsaturated carboxylic acids and derivatives thereof.

As a method for preparing such an ultrahigh molecular weight polyolefin composition, the following method may be mentioned. (1) A method in which either or both of the ultrahigh molecular weight polyolefin (A) and the polyolefin (B) are modified with the modifying monomer (C), and then both are mixed in the above content ratio.

(2) A method of mixing the ultrahigh molecular weight polyolefin (A) and the polyolefin (B) and then modifying the mixture with the modifying monomer (C). (3) When the olefin is polymerized, a multi-stage polymerization using a specific Ziegler type catalyst is performed to produce a mixture containing the ultrahigh molecular weight polyolefin (A) and the polyolefin (B) in the above content ratio, and then the mixture is modified. A method of modifying with a monomer (C) for use.

The method for preparing a mixture containing the ultrahigh molecular weight polyolefin (A) and the polyolefin (B) by the above multi-step polymerization is a highly active solid titanium catalyst component (a) containing magnesium, titanium and halogen as essential components. )
And a method of multi-step polymerizing an olefin in the presence of a Ziegler type catalyst formed from the organoaluminum compound catalyst component (b). For example, first, in a one-step polymerization step, an olefin is polymerized to produce the above ultrahigh molecular weight polyolefin (A), and in another step of the polymerization step, an olefin is polymerized in the presence of hydrogen to obtain a polyolefin (B). By producing, it is possible to obtain a mixture containing the above-mentioned ultrahigh molecular weight polyolefin (A) and polyolefin (B).

The Ziegler type catalyst used in this multi-stage polymerization is a catalyst having a specific property which is basically composed of a solid titanium catalyst component and an organoaluminum compound catalyst component. As this solid titanium catalyst component, for example, a highly active fine powdery catalyst component having a narrow particle size distribution and an average particle size of about 0.01 to 5 μm and having a form in which a few microspheres are adhered is used. Is preferred. The highly active fine powder titanium catalyst component having such properties is obtained by contacting a liquid titanium compound with a liquid titanium compound in the solid titanium catalyst component described in JP-A-56-811, for example. It can be produced by strictly adjusting the deposition conditions when the solid product is deposited. For example, JP-A-56-811
In the method disclosed in the publication, a hydrocarbon solution in which magnesium chloride and a higher alcohol are dissolved is mixed with titanium tetrachloride at a low temperature, and then the temperature is raised to about 50 to 100 ° C. to precipitate a solid product. At this time, a trace amount of about 0.01 to 0.2 mol of monocarboxylic acid ester is allowed to coexist with 1 mol of magnesium chloride, and the precipitation is performed under a strong stirring condition. If necessary, it may be washed with titanium tetrachloride. In this way, the activity,
It is possible to obtain a solid catalyst component that satisfies both the particle state. This catalyst component contains, for example, about 1 to 6% by weight of titanium and has a halogen / titanium (atomic ratio) of about 5 to 9%.
0, magnesium / titanium (atomic ratio) is in the range of about 4 to 50.

Further, the slurry of the solid titanium catalyst component obtained as described above is sheared at a high speed and has a narrow particle size distribution and usually has an average particle size of 0.0.
Those composed of microspheres in the range of 1 to 5 μm, preferably 0.05 to 3 μm are also suitably used as the highly active fine powder titanium catalyst component. As a method of high-speed shearing treatment, for example, a method of treating a slurry of solid titanium catalyst component in an inert gas atmosphere using a commercially available homomixer for an appropriate time is adopted. At that time, in order to prevent the deterioration of the catalytic performance, a method of adding an organoaluminum compound in an equimolar amount to titanium in advance can also be adopted. Further, a method of removing coarse particles from the treated slurry with a sieve can be adopted. By these methods, the highly active fine powdery titanium catalyst component having the fine particle size can be obtained.

Using the highly active fine powdery titanium catalyst component and the organoaluminum compound catalyst component, if necessary, together with an electron donor, pentane, hexane, heptane,
In a hydrocarbon solvent such as kerosene, for example, ethylene alone or a monomer mixture containing ethylene as a main component is slurry-polymerized in a multi-stage polymerization step of at least two stages under a temperature range of 0 to 100 ° C. By doing so, a mixture of ultrahigh molecular weight polyethylene and polyethylene can be produced.

Specific examples of the organoaluminum compound catalyst component used include trialkylaluminums such as triethylaluminum and triisobutylaluminum; dialuminum chlorides such as diethylaluminum chloride and diisobutylaluminum chloride; alkyls such as ethylaluminum sesquichloride. Examples thereof include aluminum sesquichloride, and these may be used alone or in combination of two or more.

In this multi-stage polymerization step, a multi-stage polymerization apparatus in which at least two or more polymerization vessels are connected in series is usually employed. For example, two-stage polymerization method, three-stage polymerization method, ... ... An n-stage polymerization method is performed. It is also possible to carry out the multi-stage polymerization method by a batch polymerization method in one polymerization tank. At least one of this multi-step polymerization process
It is necessary to produce a specific amount of ultra high molecular weight polyolefin in each polymerization tank. The polymerization step for producing the ultrahigh molecular weight polyolefin may be the first step, an intermediate polymerization step, or a plurality of steps of two or more steps. .. It is preferable to generate the ultrahigh molecular weight polyolefin (A) in the first stage polymerization step from the viewpoint of the polymerization treatment operation and the control of the physical properties of the generated polyolefin. In this polymerization step, 15-40% by weight of the olefin polymerized in all steps
Is polymerized to produce an ultrahigh molecular weight polyolefin (A) having a predetermined intrinsic viscosity [η]. Furthermore, it is preferable to polymerize 18 to 37% by weight, particularly 21 to 35% by weight, of the monomer to be polymerized in the entire polymerization step to produce an ultrahigh molecular weight polyolefin (A) having a predetermined intrinsic viscosity.

In this multi-step polymerization step, in the polymerization step for producing the ultrahigh molecular weight polyolefin (A), the polymerization is carried out in the presence of a specific Ziegler type catalyst comprising the above-mentioned highly active titanium catalyst component and organoaluminum catalyst component. .. This polymerization can be carried out by a gas phase polymerization method or a liquid phase polymerization method. In any polymerization method, in the polymerization step for producing the ultrahigh molecular weight polyolefin (A), the polymerization reaction is carried out in the presence of an inert medium, if necessary. For example, in the gas phase polymerization method,
If necessary, it is carried out in the presence of a diluent consisting of an inert medium, and in the liquid phase polymerization method, if necessary, it is carried out in the presence of a solvent consisting of an inert medium.

In the polymerization step for producing the ultrahigh molecular weight polyolefin (A), a highly active titanium catalyst component as a catalyst, for example, about 0.001 to 20 mg of titanium atom per liter of medium, and particularly about 0.005.
It is preferable to use -10 milligram atoms and an organoaluminum compound catalyst component in a ratio such that Al / Ti (atomic ratio) is about 0.1 to 1000, particularly about 1 to 500.
The temperature in the polymerization step for producing the ultrahigh molecular weight polyolefin (A) is usually in the range of about -20 to 120 ° C, preferably about 0 to 100 ° C, particularly preferably about 5 to 95 ° C. Further, the pressure of the polymerization reaction may be in a pressure range capable of performing liquid phase polymerization or gas phase polymerization at the above temperature, and for example, from atmospheric pressure to about 100 kg / cm ² , preferably from atmospheric pressure to
It is in the range of about 50 kg / cm ² . The polymerization time may be set so that the amount of all-polymerized polyolefin produced is about 1000 g or more, preferably about 2000 g or more per 1 mg of titanium in the highly active titanium catalyst component. In addition, in the polymerization step, in order to produce the ultra-high molecular weight polyolefin (A), it is preferable to carry out the polymerization reaction in the absence of hydrogen. Furthermore, after carrying out the polymerization reaction,
It is also possible to isolate the polymer once under an atmosphere of an inert medium and store it.

Specific examples of the inert medium used in the polymerization step for producing the ultra high molecular weight polyolefin (A) include aliphatic carbonization such as propane, butane, pentane, hexane, heptane, octane, decane and kerosene. Hydrogen; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloroethane, methylene chloride and chlorobenzene. These are 1
They may be used alone or in combination of two or more. Aliphatic hydrocarbons are particularly preferable.

Further, in the method of the present invention, in a polymerization step other than the polymerization step for producing the above ultrahigh molecular weight polyolefin (A), the remaining monomer is subjected to a polymerization reaction in the presence of hydrogen to produce a low molecular weight polyolefin. (B) is generated. If the polymerization step for producing the ultra-high molecular weight polyolefin (A) is the first-stage polymerization step, the second and subsequent polymerization steps are the steps for producing the low-molecular-weight polyolefin (B) performed in the presence of hydrogen. is there. When the polymerization step of the low molecular weight polyolefin (B) is located after the production step of the ultra high molecular weight polyolefin (A), the ultra high molecular weight polyolefin is included in the polymerization step of the low molecular weight polyolefin (B). When the reaction mixture containing (A) is fed and the polymerization step of this low molecular weight polyolefin (B) is located before the polymerization step in which the ultra high molecular weight polyolefin (A) is produced, it is produced in the previous step. The low molecular weight polyolefin (B) and the ultrahigh molecular weight polyolefin (A) are supplied, and in each case, the polymerization is continuously carried out. At that time, in the polymerization step, usually,
A raw monomer mixture and hydrogen are supplied. When the polymerization step is the first step polymerization step, a catalyst comprising the highly active titanium catalyst component and the organoaluminum compound catalyst component is supplied, and when the polymerization step is the second or subsequent polymerization step. The catalyst contained in the polymerization reaction mixture produced in the previous step can be used as it is, or the high activity titanium catalyst component and / or the organoaluminum compound catalyst component can be additionally supplemented if necessary. Good.

The hydrogen supply rate in the polymerization steps other than the above-mentioned ultrahigh molecular weight polyolefin (A) production step is
It is usually in the range of 0.01 to 50 mol, preferably 0.05 to 30 mol, relative to 1 mol of the monomer supplied to the polymerization step.

The concentration of each catalyst component in the polymerization reaction mixture in the polymerization tank in the polymerization step other than the polymerization step for producing the ultrahigh molecular weight polyolefin (A) is such that the treated catalyst is treated with titanium atom per 1 liter of the polymerization volume. Converted to about 0.
001 to 0.1 milligram atom, preferably about 0.00
5 to 0.1 milligram atom, polymerized Al / Ti
(Atomic ratio) is about 1-1000, preferably about 2-500.
It is preferable to adjust so that If necessary, an organoaluminum compound catalyst component may be additionally used. In addition to the above, a hydrogen / electron donor, a halogenated hydrocarbon and the like may coexist in the polymerization system in order to control the molecular weight, the molecular weight distribution and the like.

The polymerization temperature is within a temperature range in which slurry polymerization or gas phase polymerization is possible, and is about 40 ° C. or higher, more preferably about 50 to 100 ° C. The polymerization pressure is, for example, from atmospheric pressure to about 100 kg / cm ² , particularly from atmospheric pressure to about 5.
A range of 0 kg / cm ² is recommended. It is preferable to set the polymerization time such that the amount of the polymer produced is about 1000 g or more, and particularly preferably about 5000 g or more, per milligram atom of titanium in the titanium catalyst component.

Polymerization steps other than the polymerization step for forming the ultrahigh molecular weight polyolefin (A) can be similarly carried out by a gas phase polymerization method or a liquid phase polymerization method.
Of course, different polymerization methods may be adopted in each polymerization step. Among the liquid phase polymerization methods, the slurry suspension polymerization method is preferably adopted. In any case, in the polymerization step, the polymerization reaction is usually carried out in the presence of an inert medium. For example, the gas phase polymerization method is carried out in the presence of an inert medium diluent, and the liquid phase slurry suspension polymerization method is carried out in the presence of an inert medium solvent. As the inert medium, the same inert media as those exemplified in the polymerization step for producing the ultrahigh molecular weight polyolefin (A) can be exemplified.

The intrinsic viscosity [η] c of the mixture of the ultrahigh molecular weight polyolefin (A) and the polyolefin (B) obtained in the final polymerization step is usually 3.5 to 15 dl /
g, preferably 4.0 to 10 dl / g, the melting torque is
Usually, it is 4.5 Kg · cm or less.

The multi-stage polymerization can be carried out in any of a batch system, a semi-continuous system and a continuous system.
As a method for modifying the composition containing the ultrahigh molecular weight polyolefin (A) and / or the polyolefin (B) or both components with the modifying monomer (C), various conventionally known methods can be adopted. For example, the ultrahigh molecular weight polyolefin (A) and / or the polyolefin (B), or a composition containing both components is suspended or dissolved in a solvent, and usually at a temperature of 80 to 200 ° C. And a method of graft-copolymerizing by adding and mixing a polymer and a radical polymerization initiator, or the like, or a melting point or higher, for example, 180
Examples include a method of bringing the modifying monomer (C) into contact with the radical polymerization initiator under melt-kneading at a temperature of up to 300 ° C.

Specific examples of the solvent used include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and decane; alicyclic rings such as cyclohexane and methylcyclohexane. Group hydrocarbon solvents; chlorinated hydrocarbon solvents such as trichloroethylene, perchloroethylene, dichloroethylene, dichloroethane, chlorobenzene; aliphatic alcohol solvents such as ethanol and isopropanol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, Examples thereof include ester solvents such as methyl acetate, ethyl acetate and butyl acetate. These solvents may be used alone or in combination of two or more.

Examples of radical polymerization initiators include radical initiators such as organic peroxides and azo compounds. Specific examples of the organic peroxide include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioyl peroxide, di-t-butyl peroxide, dicumyl peroxide, (2,5- Dimethyl-
2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, lauroyl peroxide, t-butylperoxyacetate, 2,5 -Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxyphenylacetate, t-butylperoxy-s-octate, t -Butyl peroxypivalate, cumyl peroxypivalate, t-butyl peroxyethyl acetate and the like can be mentioned.

Specific examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyrate. These radical initiators may be used alone or in combination of two or more.

In the ultrahigh molecular weight polyolefin composition used in the present invention, the grafting amount of the modifying monomer (C) is 100% by weight of the total amount of the ultrahigh molecular weight polyolefin (A) and the polyolefin (B). 0.2 ~
The ratio is preferably 2.0% by weight, particularly 0.7 to
A proportion of 1.3% by weight is preferred.

In the present invention, a filler and a coloring agent are added to the ultra high molecular weight polyolefin composition in the same manner as in the above-mentioned polyolefin thermoplastic elastomer.
It can be included within the range not impairing the object of the present invention.

Further, in the present invention, in the ultrahigh molecular weight polyolefin composition, as in the case of the above-mentioned thermoplastic polyolefin elastomer, a phenol type, a sulfite type, a phenylalkane type, a phosphite type,
Known heat stabilizers such as amine stabilizers; antiaging agents;
Additives such as weather resistance stabilizers; antistatic agents; lubricants such as metal soaps and waxes can be included in the proportions usually used in the production of olefin plastics or olefin copolymer rubbers.

In the present invention, the ultrahigh molecular weight polyolefin composition comprises the ultrahigh molecular weight polyolefin composition and the slip resin in a total amount of 1 of these components.
2 to 90 parts by weight, preferably 3 to 90 parts by weight
70 parts by weight, more preferably 5 to 50 parts by weight are used.

By blending the ultrahigh molecular weight polyolefin composition in the slip resin in the above proportion, the sliding characteristics of the slip resin can be improved. Lubricating Resin Examples of the lubricating resin used in the present invention include polyamide resin, thermoplastic polyurethane resin and thermoplastic polyester resin.

Specific examples of the polyamide resin include various nylons such as 6-nylon and 6,6-nylon. The thermoplastic polyurethane resin is preferably a resin having excellent water resistance, oil resistance and scratch resistance. Any polyurethane resin that is thermoplastic and has the above-mentioned properties can be used as the slip resin of the present invention.

As the above thermoplastic polyester resin,
Specifically, polyethylene terephthalate (PET),
Examples include polybutylene terephthalate (PBT) and polyethylene isophthalate (PEI).

In the present invention, the slip resin is 9 parts by weight based on 100 parts by weight of the total amount of these components constituting the layer comprising the ultrahigh molecular weight polyolefin composition and the slip resin.
It is used in a proportion of 8 to 10 parts by weight, preferably 97 to 30 parts by weight, and more preferably 95 to 50 parts by weight.

In addition, the above ultrahigh molecular weight polyolefin composition may include, if necessary, a mineral oil softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antiaging agent, a filler, a colorant, a lubricant. Can be added within a range that does not impair the object of the present invention.

In the glass run channel according to the present invention, the draining section 3 is preferably made of the same material as the main body 2. When the main body 2 is made of a thermoplastic polyolefin-based elastomer, if the draining portion 3 is also made of the same material, it is sufficiently practical in terms of durability and bonding strength with the slip resin layer 9. ..

Shark skin (shark skin) that can be used in the glass run channel according to the present invention can be exhibited at the time of molding by appropriately selecting the properties of the raw material polyolefin thermoplastic elastomer.

The appearance of the obtained shark skin is different from the melt fracture which is sometimes seen during extrusion molding of resin or elastomer, and the skin of the molded product is periodically roughened to form fine irregularities.

Further, it is necessary that the sharkskin is exposed on the surface of the slippery resin layer 9 provided on the sharkskin. The thickness of the slippery resin layer 9 is usually 3 to 50 μm.
It is laminated so that it becomes m. Further, in the present invention, the thickness of the slipping resin layer 9 can be further increased or decreased as necessary.

Since the portion where the drainage part 3 contacts the window glass 12 is generally different when the window glass 12 enters and leaves the window glass 12, coating with the ultrahigh molecular weight polyolefin composition and the slip resin and, if necessary, The sharkskin to be formed is preferably formed in a relatively wide area of the drainage section 3.

Further, in the specific example shown in FIG. 1, there is a portion 16 inside the main body 2 that comes into contact with the end portion of the window glass, and this portion 16 also has the surface of the main body 2 made of a thermoplastic polyolefin elastomer. A slipping resin layer 9 composed of an ultrahigh molecular weight polyolefin composition and a slipping resin can be provided.

Further, in the present invention, naps may be present on the surface of the slip resin layer 9. As the method for decorating the raised hair, (a) a method of buffing with emery paper to raise and decorate the surface of the slippery resin layer, and (b) passing through a needle cloth roll to raise the surface of the slippery resin layer A method for decorating, (c) a method for raising and decorating the surface of the slippery resin layer by sanding with a belt sander, a drum sander, or the like, (d) a thermal fineness described in JP-A-62-275732 Conventionally known raised decorating methods such as a method of colliding a body to decorate the surface of the slippery resin layer are raised.

[0109]

According to the present invention, it is possible to omit all the steps of applying the adhesive, hardening or baking the adhesive, and embossing steps before and after the step. As a result, the number of steps can be reduced. In addition, because the working time can be shortened, it is possible to manufacture a glass run channel with excellent economical efficiency, durability, close contact with the window glass when closed, and light sliding when opening and closing. A glass run channel having excellent properties can be provided.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0111]

Example 1 Ethylene / propylene / 5-ethylidene-2-
Norbornene copolymer rubber [ethylene content 70 mol%, iodine value 12, Mooney viscosity ML _{1 + 4} (100 ° C)
120] 75 parts by weight and polypropylene [MFR 13 g
/ 10 minutes (ASTM D 1238-65T, 230
)) And a density of 0.91 g / cm ³ ] 25 parts by weight with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and then the kneaded product is passed through a roll to form a sheet, which is then cut with a sheet cutter. It was cut into square pellets.

This square pellet was filled with divinylbenzene.
5 parts by weight and 0.3 parts by weight of 1,3-bis (t-butylperoxyisopropyl) benzene were added and mixed by stirring with a Henschel mixer.

Next, this mixture was extruded at a temperature of 220 ° C. in a nitrogen atmosphere using a uniaxial extruder having L / D = 30 and a screw diameter of 50 mm to obtain a thermoplastic polyolefin-based elastomer.

The gel content of the obtained thermoplastic polyolefin-based elastomer was 97% by weight as determined by the above method. This polyolefin-based thermoplastic elastomer was coextruded at a temperature of 230 ° C. to form a glass run channel body and a draining portion, and the surface thereof had an intrinsic viscosity [η] of 21 dl / g measured in a decalin solvent at 135 ° C. Ultra high molecular weight polyethylene 2
5% by weight and low molecular weight polyethylene 75 having an intrinsic viscosity [η] of 1.5 dl / g measured in a decalin solvent at 135 ° C.
And an ultra high molecular weight polyethylene composition consisting of 1 wt% [maleic anhydride content: 1 wt%, intrinsic viscosity [η] measured in 135 ° C. decalin solvent: 6.4 dl / g, density:
0.965 g / cm ³ ] 20 parts by weight and 6-nylon [trade name Amilan CM-1007, manufactured by Toray Industries, Inc.] 80
A mixture obtained by previously mixing 1 part by weight with a Henschel mixer was extrusion-laminated at 250 ° C. to obtain a glass run channel of the present invention.

The obtained glass run channel has a substantially trapezoidal shape, and the total length of the inclined portion and the horizontal portion of the glass run channel 1 fixed to the window frame 13 in FIG. The length of the part is 90 mm,
At the bottom of the main body 2, the outer width is 15 mm, and the outer height of the side is 20 m.
The length of the drainage part 3 was 10 mm, the length was approximately equal to the cross-sectional shape shown in FIG. 1, and the thickness of the layer composed of the ultrahigh molecular weight polyethylene composition and 6-nylon was 30 μm on average.

The time required for forming the glass run channel was 0.2 minutes per 1 m shorter than the time required by the conventional method, which was 60% of the time required by the conventional method. The glass run channel thus obtained was attached to a test window frame, and a 3.2 mm-thick window glass was fitted to perform a durability test (upper and lower window glass repeated tests). As a result, this glass run channel survived the 50,000 times window glass up-and-down repeated test, and maintained the function as a glass run channel. However, the conventional glass run channel (the window glass sliding part has a laminated structure in which a nylon film is adhered to the soft vinyl chloride resin layer)
After 000 cycles, the contact surface of the window glass was broken, and as a result, the frictional resistance with the window glass was remarkably increased and it became unusable.

[0117]

[Example 2] Ethylene / propylene / 5-ethylidene-2-
Norbornene copolymer rubber [ethylene content 70 mol%, iodine value 12, Mooney viscosity ML _{1 + 4} (100 ° C)
120] 75 parts by weight and polypropylene [MFR 13 g
/ 10 minutes (ASTM D 1238-65T, 230
)) And a density of 0.91 g / cm ³ ] 25 parts by weight with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and then the kneaded product is passed through a roll to form a sheet, which is then cut with a sheet cutter. It was cut into square pellets.

This square pellet was charged with divinylbenzene.
5 parts by weight, 0.3 parts by weight of 1,3-bis (t-butylperoxyisopropyl) benzene, and 0.5 parts by weight of maleic anhydride were added and mixed by stirring with a Henschel mixer.

Then, this mixture was extruded at a temperature of 220 ° C. in a nitrogen atmosphere using a uniaxial extruder having L / D = 30 and a screw diameter of 50 mm to obtain a graft-modified polyolefin thermoplastic elastomer.

The gel content of the obtained graft-modified polyolefin thermoplastic elastomer was 96% by weight as determined by the above method. This polyolefin-based thermoplastic elastomer was coextruded at a temperature of 230 ° C. to form a glass run channel body and a draining portion, and the surface thereof had an intrinsic viscosity [η] of 21 dl / g measured in a decalin solvent at 135 ° C. Ultrahigh molecular weight polyethylene composition consisting of 25% by weight of ultrahigh molecular weight polyethylene and 75% by weight of low molecular weight polyethylene having an intrinsic viscosity [η] of 1.5 dl / g measured in a decalin solvent at 135 ° C. [maleic anhydride content Intrinsic viscosity [η] measured in decalin solvent at 135 ° C .: 1 wt%: 6.4 dl /
g, density: 0.965 g / cm ³ ] 20 parts by weight, 6-
Nylon [Brand name Amilan CM-1007, Toray Industries, Inc.
80 parts by weight was mixed in advance with a Henschel mixer to obtain a mixture, which was coextrusion laminated at 250 ° C. to obtain a glass run channel similar to that of Example 1.

The molding time of the obtained glass run channel was 60% of the time required by the conventional method, and the window glass up-and-down repeated test withstood 50,000 times.

[0122]

Example 3 In Example 2, instead of 6-nylon, a polyurethane resin [Nippon Polyurethane Industry Co., Ltd.] was used.
Manufactured by Polyurethane P26 SR NAT]
The same procedure as in Example 2 was performed. The obtained glass run channel survived 50,000 times of repeated upper and lower windshield tests.

[0123]

Example 4 Example 6 was repeated except that a polyethylene terephthalate resin having an intrinsic viscosity [η] of 1.0 dl / g measured in a 25 ° C. orthochlorophenol solution was used in place of 6-nylon. The same procedure as in 2 was performed. The obtained glass run channel survived 50,000 times of repeated upper and lower windshield tests.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a glass run channel according to the present invention.

FIG. 2 is an enlarged sectional view of a contact portion of the glass run channel shown in FIG. 1 with a window glass.

FIG. 3 is a diagram illustrating attachment of a glass run channel to an automobile door.

FIG. 4 is a cross-sectional view showing a state of a glass run channel when a window glass is opened.

FIG. 5 is a cross-sectional view showing a state of the glass run channel when the window glass is closed.

[Explanation of symbols]

1 ・ ・ ・ Glass run channel 2 ・ ・ ・ Glass run channel main body 3 ・ ・ ・ Drainer 4 ・ ・ ・ Contact part with window glass 7 ・ ・ ・ Polyolefin thermoplastic elastomer Base layer consisting of 8: Surface of base layer having repeating pattern of fine irregularities (provided as necessary) 9: Lubricating resin composed of ultra-high molecular weight polyolefin composition and lubricating resin Layer 10: Surface of slipping resin layer having repetitive pattern of fine irregularities (provided as necessary)

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B32B 27/36 7016-4F 27/40 B60J 10/04

Claims (1)

[Claims] 1. A glass run channel made of a polyolefin-based thermoplastic elastomer, which comprises a groove-shaped main body in a cross section and a tongue-shaped draining portion that projects from the vicinity of the top of the side wall toward the center. At least a portion of the surface of the drainage portion that can come into contact with the window glass is composed of a layer composed of an ultra-high molecular weight polyolefin composition and a slip resin laminated on a thermoplastic polyolefin-based elastomer layer, and the ultra-high molecular weight polyolefin composition (A) 90 to 10 parts by weight of an ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] of 6 dl / g or more, and (B) 10 to 90 parts by weight of a polyolefin having an intrinsic viscosity [η] of 0.1 to 5 dl / g. Parts, and the ultrahigh molecular weight polyolefin (A) and / or polyolefin (B) is an unsaturated carboxylic acid or And at least one modifying monomer (C) selected from derivatives thereof
A glass run characterized in that it is an ultra-high molecular weight polyolefin composition modified by, wherein the slipping resin is a slipping resin selected from the group consisting of polyamide resin, thermoplastic polyurethane resin and thermoplastic polyester resin. Channel.